Elastomeric composition containing a cyanoalkylamine



United States Patent 0.

Patented June 12, 1962 3,038,868 ELASTOMERIC COMPOSITION CONTAINING A CYANOALKYLAIVIENE Rene G. Jennen, Detroit, Mich, assignor to Oliver W. Burke, ha, Grosse Pointe Park, Mich. No Drawing. Filed Dec. 30, 1955, Ser. No. 556,423 6 Claims. (Cl. 260-4) This invention relates to cyanoalkylamines, and reaction products including saponification products of certain of these cyanoalkylamines, some of which are new chemicals per se, and the use of these cyanoalkylamines and their reaction products as vulcanization aids.

These cyanoalkylarnines and their reaction products can be used as vulcanization aids in combination with elastomers including synthetic elastomers and natural rubber. These synthetic elastomers, like natural rubber, are characterized in that they contain ethenoid unsaturation, C=C and are sulfur vulcanizable, as hereinafter set forth.

Further, these new vulcanization aids can be used with fillers including active fillers and with both inorganic and organic type fillers including carbon black.

The cyanoalkylamines and their reaction products can be used in combination with both elastomers and fillers, and with other compounding ingredients.

This invention relates to the compounding and vulcanization of elastomers and the resulting vulcanizates, and aims genirally to improve the same. In particular this invention aims to provide new and improved compounding recipes and new methods of vulcanization in which the vulcanization aid is from the group consisting of amines and polyamines N-substituted with cyanoalkyl groups with consequent improvement of such compound,

the workability and vulcanization thereof, and the vulcanizate therefrom.

The invention is concerned with the use of cyanoalkylamines and their reaction products to improve the compounding of elastomers containing as reinforcing agent the vinylic fillers, especially the acid and carbonyl containing vinylic fillers, of the inventions disclosed by Oliver W. Burke, Jr. in his copending applications, viz., Serial No. 378,735, Serial No. 462,611, and Serial No. 538,728, filed on September 8, 1953, October 15, 1954, and October 5, 1955, respectively, counterparts of which have issued as Belgian Patents Nos. 531,665 (British Patent No. 799,043), 542,068 and 551,532, dated Sepember 30, 1954, October 31, 1955 and October 31, 1956 respectively.

Further, this invention is concerned in part with improved compounding recipes useful for compounding elastomers reinforced with conventional reinforcing agents, such as carbon black, lignin, silica, clays, diatomaceous earths, titania, metal oxide, metal silicates, car-- bonates, and the like.

The present invention is particularly concerned with the provision of compounding recipes capable of imparting improved physifal properties (tensile strength, elongation, heat building under flexure) to elastomer compounds containing tf le said conventionally used reinforcing agents as well as to elastomer compounds containing the vinylic fillers of said copending applications.

Also this invention is concerned with the development of tackiness, especially in synthetic elastomers, e.g., of the GR S type, which tackiness is important in the fabrication of elastomer end items wherein mutual adhesion of elastomer components or coated components is required prior to vulcanization.

In addition, this invention is concerned with the improvement in curing rates of elastomer compounds so that a fiat curve or plateau is obtained when the curing timetensile properties relationship is represented graphically. This is of importance industrially in assuring the attainment of near optimum tensile properties of the vulcanizate over a fairly broad range of curing times and temperatures when the cyanoalkyl-amine curing aids of this invention are appropriately incorporated.

The invention is further concerned with the provision of amines active in vulcanization that melt below 285 F. and do not boil below 320 F., and that are'soluble in the elastomer components of vulcanization recipes.

The invention is also concerned with the provision of new and useful cyanoalkyl-substituted-polyamines that produce fiat cures, and with the provision of new and useful cyanoalkyl-substituted-polyamines that are precombinable advantageously with other ingredients of a compounding recipe to form a new compounding material, and with methods for preparing such new cyanoalkylsubstituted-polyamines.

TYPICAL KNOWN ELASTOMER CURING PROCEDURES It is well known in the art to vulcanize unsaturated elastomers, with or without fillers, by reaction with sulfur in the presence of curing additives to accelerate the rate of vulcanization and to develop useful tensile properties of the elastomer compound by such vulcanization. A typical compounding recipe for curing or vulcanizing a G114 type elastomer is taken as an example from page 123, The Vanderbilt Rubber Handbook, published With this formula employing GR-S elastomer an optimum tensile strength of 3010 p.s.i. at an elongation of 460% Was obtained and a 300% modulus of 1640 p.s.i.

With natural rubber and sulfur and no other ingredicuts, a cure is attained in six hours at 287 F. and the vulcanization reaction is essentially the formation of sulfur cross-links between elastomer molecules. The carbon black (cf. Recipe 1) is a high-surface reinforcing material which forms strong bonds with the elastomer molecules. The zinc oxide in conventional recipes is added to accelerate the elastomer-sulfur cross-linking reaction (Vanderbilt Rubber Handbook, page 98), and with natural rubber the rate is increased about 15% so that five hours instead of six hours may serve to cure the rubber when the cure is effected with natural rubber, carbon black, sulfur and zinc oxide. To further accelerate the reaction an organic accelerator is conventionally used -(such as benzothiazyl disulfide of Recipe 1) together with stearic acid as an activator for the accelerator. With such acceleration and stearic acid activation, the curing time can be cut to one hour. (Also the use of the accelerator permits the use of as little as 1.5 pts. of sulfur to effect good vulcanization.) The use of a small amount of an ultra' accelerator (cumate in the above mentioned recipe may be replaced with tetraethylthiuramdisulfide) is important to attain still shorter cure times of the order of 15in 45 minutes. This is especially necessary to obtain optimum cures in reasonable time with formulae such as Recipe 1 and elastomer stocks showing acidity, e.g.,

3 from the reinforcing agents (such as EPC, MPC, HPC carbon blacks, or such as the acid vinylic fillers of said copending patent applications of O. W. Burke, Ir), or from any other acid ingredient.

In curing GR$ elastomers, the addition of the stearic acid component to the curing system is not always necessary. In compounding natural rubber with the vulcanization aids of this invention the use of stearic acid is not always necessary and depends on the types of additional accelerators used. Also plasticizers, softeners and tackifiers are often used in compounding GR-S elastomers to improve tack and processibility. A final ingredient, an antioxidant, is ordinarily incorporated into the compound ing recipe to protect against oxidative deterioration during processing or storage both prior to or following vulcanization.

Superior physical properties are obtained from GRS and like elastomers by variation of the compounding formula, and Recipe 2, set forth below, is a typical, heretofore known, tire tread recipe herein employed in the preparation of the controls and, with inclusion of the new ingredients, for the compounding of the illustrative examples of the present invention.

Recipe 2 Ingredients: Parts GR-S 1500 100 Reinforcing agent 1 20 to 50 Antioxidant (AgeRite Resin D) 1 Zinc oxide 3 Petroleum oil softener /2 Circosol ZXH, /2

'Paraflux 2016) 5 Stearic acid activator 1 Organic accelerator N-cyclohexyl-Z-benzothiazole sulfenarnide (Santocure) Sulfur 1 Variable, depending on type.

A typical cure with GR-S 1500, compounded according to Recipe 2 With 50 parts high abrasion furnace black (e.g., Philblack O) is represented by the following data:

Compound Mooney, ML4 70 7O 7O 70 70 Cure time at 285 F., min.-. 30 60 75 90 120 Tensile strength, p.s i 2, 500 3, 000 3, 300 3, 400 3, 200 Elongation, percen 650 550 500 500 470 300% modulus, p.s.i 1,450 1, 700 1, 800 2, 000 2, 200 Shore A hardness 55 59 63 65 64 GENERAL DESCRIPTION 1 have now discovered that incorporation of cyanoalkylamines, and particularly of polyamines substituted with cyanoalkyl groups, and especially with alpha-cyanoalkyl groups, show remark-able improvement in the stock and in the vulcanizates therefrom. Amines alkyl substituted, such as aliphatic amines, have low boiling points and hence have high vapor pressures at ordinary temperatures, causing them to volatilize readily from the stock. They do not impart tack to the stock, and they produce peaked curing curves (Table 6). I have discovered that the corresponding cyanoalkyl substituted amines are as active in promoting the cure as the high volatile amines, and are advantageous in that they have high boiling points, above 320- F., and do not volatilize from the stock in storage or on the mill. In addition, as could not be anticipated, they contribute tackiness to the that are not cyano" AMINES EMPLOYABLE FOR CYANOALKYL SUBSTITUTION with cyanoalkyl groups are formula As amines for substitution included those of the general in which R and R are hydrogen or any organic radical. Thus the amines employable for cyanoalkyl substitution in accordance with this invention include both the primary and secondary amines. When R and/or R are hydrogen the additional He also may be substituted with the cyanoalkyl radical.

When the amine is a polyamine, one of the radicals R or R may contain one or more additional amine or imino groups, and the hydrogens of such groups can also be cyanoalkyl-substituted in accordance with this invention.

The organic radicals R or R may be alkyi groups, oxaalkyl groups, and the like, and the aliphatic chain may carry a homocyclic or a heterocyclic ring.

Examples of the monoand polyamines represented by the above formula are set forth in Tables 1 and 2, respectively.

MATERIALS EMPLOYABLE TO SUPPLY THE CYANOALKYL COMPONENTS For producing the alpha-cyanoalkyl substituents, any cyanohydrin may be employed, of the general formula Common R3 R4 Prepared iromcyanohydrin (-HCN) name H H Methanol HON. Formaldehyde 7 6 t g ycom n e. OH --H Ethanal HCN Acetaldehyde Ti -W ac om r! e. CI;I CH 2-propanone HON. Acetone HGN. -CH C H Methyl phenyl Aoetophenone ketone -I-I ON A -HCN. CH3 G(OH ):OH 2-1nethy]-buten-3"' one HON, etc.

These cyanohydrins react with the amines by substitution of one or more of the hydrogens of the NH group, as:

For producing the beta-nitri le subs-tituents, acryloand meth-acrylo-nitrile may be employed. In this instance when the acrylonitrile (ethenyl or vinyl cyanide, CH :CH.CN) reacts with the amine (HNR R addition takes place at the double bond, hydrogen attaching to the alpha carbon, and the amine radical (R,,NH) attaching to the beta carbon, producing a beta-cyanoalky1 substituted amine of the type:

When the alkenyl cyanide is methacrylonitrile, the reaction the same, producing the homologous beta-cyanoalkylsubstituted amine:

Examples of these nitrile producing materials are included in Tables 1 and 2, and in Tables 3 to 38.

PREPARATION OF THE CYANOALKYL- SUBSTITUTED AMINES The alpha-cyanoalkyl-substituted amines are simply prepared by the reaction of the amines with the cyanohydrin at 80 C., in benzene, say, as solvent, as follows:

R NR H+cyanohydrin- R NR cyanoalkyl+H O (6) and when R is hydrogen: R NH-cyanoalkyH-cyanohydrin and when R is also hydrogen:

NH (cyanoalkyl) +cyanohydrin- N(cyanohydrin) 3 (8) The water is removed by azeotropic distillation from the reaction mixture. The cyanoalkyl groups may be identical, or all different, or two identical, and one dissimilar, as desired.

The N-beta-cyancalkyl-substituted amines are also easily prepared by reaction of the alkenyl nitrile with the amine as follows:

in which R is hydrogen or an organic radical such as alkyl, aryl, etc., and R and R are the radicals of the, amine.

As a key to the nomenclature employed herein may be cited the following:

TYPICAL ALPHA-CYANOALKYL-SUBSTITUTED (from :glyconitrile) Cyanomethyl-isopropylamine, or with two substitutions:

Di-cyanomethyl-isopropylamine.

Or if ammonia is employed (R and R both hydrogens) the tricyanoalkyl amine can be formed.

(from methyl lactonitrile) N -(a1pha-cyano-alpha-methyl-ethyl)-phenylenediamine, or with more substitutions:

N,N -di( alpha-cy ano-alpha-methylethyl) -phenylene diamine,

- N ,N,N-,-trialph acyano-alpha-methylethyl) -phenylenediamine, N,N,N,N-tetraalpha-cyano-alpha-methyl-ethyl) phenylenediamine.

H E-C-H (from aceto- Qifluwnwnm],

henone cyauol ydrin) CN (12 N-( alpha-cyano-alpha-phenyl-ethyl) -disopropyl amine t CO Ha (from Z-methl- H3C-C--NH.CH2.CH: CH1

buten-3-0ne cyanohydrin) O N (13 N-( alpha-cyano-alpha-methybbeta-methyl-allyl) -allyl amine,

Dialphacyano-alph a-methyl-b eta-methyl-al-lyl) -allyl amine.

TYPICAL BETA-CYANOALKYL-SUBSTITUTED AMINES Beta-cyanoalkyl-amine (from acrylonitrile and ammonia) Mono-, di-, and

tri-beta-cyanoalkyl amines are made (14) Beta-cyanoethyl-isopropylamine,

(from methene-diamine) C N (from acrylonitrile and isopropylamme) N (beta-cyanopropyl) -phenylenediamine,

N,N'-di (beta-cyanopropyl) -phenylenediamine, N,N,N-tri (beta-cyanopr opyl) -phenylenediamine, N,N,N' ,N-tetra (b eta-cyanopropyl -phenylenediamine To further exemplify the derivation and nature of new vulcanization aids of the present invention, Tables 1 and 2 set forth respectively, reaction of typical cyanohydrins with typical amines and polyamines, and physical properties of the resulting cyanoalkyl-substituted amines and polyamines. It will be, noted from Examples 2-11 to 2-13 that mixed polyethylene-polyamines yield substituted amine product similar to those obtained with the individual amines, and which, as is shown in Table 8, are valuable vulcanization aids. When lactontirile is used with the amines as illustrated in Tables 1 and 2, then the resultant cyanoalkyl amines are N-substituted-alphaamino-propionitriles.

Before listing the remaining tables to constitute an index thereto, the following points should be noted:

(1) The more volatile unsubstituted aliphatic amines, e.g., methyl-, ethyl-, propyl-, butyl-, ally-1-, heptyl-, tertoctyl-amines, etc., developed good tensile properties in the elastomers when curing was carried out soon after mixing small amounts of such amines with the elastomer compound, but if the so prepared compounds were stored for more than 12 hours the optimum tensile properties were no longer obtainable.

(2) In no instance was tackiness or the desired flat curing curve obtained with these prior known unsubstituted aliphatic amines.

(3) When higher alkyl and aryl amines not substituted with cyano-alkyl groups were employed (e.g., higher alkyl amines such as stearylamine, C to C alkyl amines, terpene amines such as rosinamine, etc. and arylamines such as phenyl-beta-naphthylamine, diphenylamine, aniline, and other aryl amines, as known to the art) the novel results obtained with the cyanoalkyl substituted amines in accordance with this invention also could not be attained, and the amines tended to act as plasticizer of the elastomer.

(4) When similar amines and polyamines N-substituted with cyanoalkyl groups were employed in accord- --7 ance with the present invention, however, the cures were improved, tackiness was imparted to the stocks, and, with polyamines substituted with alpha-cyanoalkyl, the greatly to be desired fiat cures were obtained.

ing, and polymerizable through, at least two ethenoid groups in non-conjugated relation.

(5) The amounts of cyanoalkylanrines required to 5 practice this invention vary as a result of a number of Table Amine Elastomer factors: among such factors the type of reinforcing filler in the elastomer compounds, the acidity or pH of the 3 Cyanoalkyl-mono Non-acidic, carbon black, qR-s. compound in the absence of the amine and the nature of 4 g fi vmyhc finer the cyanoalkyl amine employed, etc., are of especial im- 5 do N i ae id, polar vinylic filler, portance- Whlle stock Contalnlng carboxyl or q y Unsubstituted Acidic n filler, GR S (peaked groups requires somewhat more of the cyanoalkylamine, cure). the definite improvement in the vulcanization resulting gf'fig i fl'l'jfii jfi i ffih: g8: from such stock justifies its use and the augmented use of (ly gnot t ilryi iu s radical Do,

, v 0 er aria yrnono. such amine. Thus, the invention includes the addition of Unsubstituted and own the cyanoalkylamiries specified herein in amounts of 0.05 10* alkglb H I D Olan -cyanoa y -H10D.0 O. to 10 parts per 100 of elastomer, depending on the other oyanoalkybmmo Carbon black, GPWS, polyacld factors mentioned. 12 0 1k 1 1 A stg k. I H fin GR 8 t I A a yanoa y-po y- .01 1c viny 0 er, s oer. 1(6) Th cyanoalkyl amines when combined with steam: ,z cyanoamyl poly Eight difierent acidic vinyhc acid and zinc 0Xld6, react therewith to form homogeneous fillers, GR-s, stock. warty materials that are especially useful in compounding g3: ig ggEGI6AH6 ;BT ga finer stockrecipes because of the ease with WhlCll they blend with the i w- 1k 1 i d 1 D ayanoa y m xe 110 y- 0. elastomer on the mill, and said reaction products do not Further cyanoalkylmixed detract from the eificacy of the cyanoalkyl amine as a p ycurin aid Other a-cyanoalkyl-poly- ,Do. g I 29 1 to .5 (a-cyanoalkyl-poly- Do. The advantages obtained on compounding, curing, and 1 andIkZI (a-cyanoalkyl- Do, testing of the elastomer yulcanizates prepared with the 2 1g; gamyanoalkyly D0 materials of the present invention are more readily ap- 22 o 1 I r fin parent by reference to the tables of data hereinafter. yanoa 5 3,, g g i GR-S The numerous examples set forth herein show the 0- y o a m d -cd c v yhc fi ers,GRS stock. broad ranges ofamines, cyanoalkyl-substituents, polymeric fgg gii l D0: sources of acidic groups, and natural and synthetic elas- 5*---- y Y -P Y- g i i s -S, a bon tomers to which the invention is applicable, and are set 26m" P 1; ift d GR S, acid forth in tabular form for convenience and brevity. Brief 27 d i e e a fi 3 comments accompany each table, and to afford an index 5 0 DO thereto, the tables are here listed, with note of the amines 332 g g g ig g fg n g g g f employed and the elastomers treated therein, astericks notimprove Q KZEZ Q F being sufiixed to the tables in this list that contain 3% cyaloamyl 33 ggg f fi 1d 1i data showing the flat cure obtained with the N-(alpha- 0 fill r to i a ac 0 cyanoalkyD-substituted amines, and especially with the 40 gfi -.-g ggggfgf i i g ggi 355 m??- N-(alpha-cyanoa lkyl)-substituted polyamines. In this list I 0 fine stocm p Vmy 1c and the tabulated examples, various reinforcing fillers 38 ig rubber, acid Vinylic filler are employed, e.g. carbon black, various vinylic fillers gyanoalkylpoly GETS and carbon black, and, in Tables 28-32, various other reinforcing fillers, and Cyfwvalkfl p- 211191 Acldw Vmylic filler, Stockpolywith tertiary mit Wlll be appreciated that the invention in its broader trogm aspect isnot dependent on the use of any particular cyanoalkylnvly-wlthterw tlary nitrogen. species of reinforcing filler. As hereinbefore noted, the cyano lkylpoly- M various vinylic fillers used in some of the examples are Red-nous compounds of cyanoalkyl poly-. prepared by methods set forth in the aforesaid copend- Cyanoalkylpoly. 7 7 r 27A d Do. ing applications, and as set forth in these applications, 39m" cyanoalkyl mono and Aging ofGR S1500 Stocks the vinylic fillers are insoluble, colloidal sized, crossp01y. linked polymer particles which are obtained by cross- Table I CYANOALKYL AMINES Typical Moles, Cyanohydrin Amine, 1 mol Abbrevia- Product Example tions 1-1 Lactonitrile, l Isopropyl ami 1-IP1 Yield 9%?! colorless liquid B.P. 6768 C. 25

mm. g. do 2-IP Colorless liquid.

Diisopropyl amine 1DIP D0. t-Butylamin 1TB Yield 92% colorless liquid. t-Octylamin l-TO Yield 7%)}, colorlessgiiquid B.P. 76-78 C. 35

mm. g. Allyl amine. 1-AL Yield 9]1H% colorless liquid B.P. -67 C. 12

mm. g. Oyclohexyl amine l-CH Yield 9IelI% colorless liquid B.P. 96-99" C. 13

mm. g. tert-Ol2-15 primary amines 1'I 12/l5 Brown-yellowliquid. tert-18 24 primary amines D0 Rosinamine D N-aminopropyl morpholine. Furfuryl amine Lactonitrile 1 Yellow; very viscous mass.

High boiling brown liquid.

sOtiligless liquid B.P. 123 C. 23 mm. Hg.

Aniline Ethanol-amino Viscous liquid. Morpholine Fluid liquid. Beta-isopropylaminopropionitrile1-- Crystalline. Beta-beta-irninobis propionitrile a Fluid.

Ammonia 3N. Crystalline. Alpha-alpha-imino bispropi0nitrile aIBPN- Do.

1 Referred to as Amitrile-LP.

Table 2 CYANOALKYL POLYAMINES Typical Moles, Cyanohydrin Amine, 1 mole Abbrevia- Product Example tions Lactonitrile, 1 Dicthylenetriamine 1-DETA...- Colorless liquid B.P. about 65C. 1 mm. Hg. Lactonitrile, 2.. ...--do 2DETA.-.. Colorless liquid B.P. 70-100C. 1 mm. Hg. Lactonitrile, 3.. -do. 3DETA--.- Viscous yellow-brown liquid. Lactonitrile, 4.. .do. 4-DET Very viscous yellow-brown liquid. Lactonitrile, 5.. .do 5-DETA..-. o. Lactonitrile, 1.. Tricthylenctctramine.- 1TETA.-.. Yellow-brown liquid not distillable. Lactonitrile, 2.- ..--.do 2TETA. Do. Lactonitrilc, 1 Tctraethylenepentamine ITEPA Do. Lactonitrile, 2. ..d 2TEPA..-- Do. Lactonitrile, 3 0 3-TEPA Do. Lactonitrilc, 1. Mixed polyethylenepolyamines 1-MPAI-I 3 Brown viscous liquid.

0. 1-MPAD..- Dark brown viscous liquid. e, ..-.do..-.. 4-MPAD..- Do. Lactonitrile, Iminobispropylaminc 1-IBPA Yellow liquid 75% distills 60-80 C. 1 mm. Hg. Lactonitrile, do 2IBIA Yellow liquid. Lactonitrile, Ethylencbisoxypropylamine. l-EBOP...- Do. Lactonitrile d0 2EBOP..-. Do. 2-18. o Hcxamctbylenediamine. 2-HMD Yellow brown liquid, partly crystallized. 2-19- Lactonitrile, -.-..do l-HMDA.-. Yellow-brown viscous liquid. 2-20. Laetonitrile, N-octyl-2-bcnz1dinc 1NO2B Solid dark. 2- -.-..do N,N d1 sec-butyl-p phenylenedi- 1-DBPD..-- Dark viscous muss.

amine. 222 Laetonitrile, 2. d0 2DBPD-... Do.

Lactonitrile, 1. Benzidine--- 1-B Dark solid. Laotonitrile, 2. ..do 2-B Do. Lactonitrile, 1-. m-Phenylenediamine- 1-MPDA--- Do. Lactonitrile, 2-.- do 2-MPDA-.. Do. Lactonitrile, 1..- p lhenylenediamine. 1PPDA.--. Do. Lactonitrile, 2 .do 2PPDA.-.. Do. Acetophenone cyano Tetraethylenepentamine 2-AC Viscous liquid. lvllelztlylisopropenylketone cy Dicthylenetriiimine 5MIPK Very viscous liquid.

y rin, 5. Lactonitrile, 4 Mixed polyethyleneamines 0 Dark brown, very viscous. Acetone cyanohydrin, Tetraethylenepentamine.- Viscous liquid. Acetone cyanohydrin, -.-..do Dr). V

Saponified 2-1EPA (2-9)- Very viscous. Tetraethylenepentamine. 2G-TEPA- Diethylenctriamine 5G-TE PA 1 Referred to as Amitrile 11-1.

2 Referred to as Arnitrile T3.

3 Referred to as Amitrile H.

4 Polyamine H special from Carbide and Carbon Chemical Co. 6 Residue Polyarnines from Dow Chemical Co.

a Polyamine '1" from Carbide and Carbon Chemical Co.

1 Referred to as Amitrile PAT.

In Tables 3 through 39, the compositions of the compounds are based on parts per hundred of clastomer. The tensile properties were obtained at 77 F. with a Scott Tensile Tester (Model ORR-5), the heat build-up values were obtained with a Goodrich Flexometer at 100 F. and the hardness values were obtained with a Shore A dnrometer at 77 F.

Turning now to the specific examples, in Table 3 a non-acid carbon black stock is compounded without amine, as a control, and with two difierent cyanoalkylsubstituted amines. The GR-S 1500 plus 50 parts of the non-acid carbon black, Philblack O, is equivalent to GRS 1600, which already contains said proportions of such carbon black. Each of the cited examples is that one of a group of examples cured to optimum tensile strength (see for example Table 9 and other tables in which several curing times are set forth to show flatness of cure). The examples of Table 3 show not only improvement in tensile values, but a marked improvement in elongation as compared with the control, and also show a marked reduction in heat build-up under fiexure of the cured elastomer.

In Table 3a it is illustrated that the tensile strength of a pt. carbon black stock can be improved by the use 6 of a cyanoalkyl persubstituted polyamine. Tensile values as high as 3510 p.s.i. were obtained in Example 3a-2, which represents a increase over the control 30-1.

The addition of the cyanoalkylated polyamine to the uncured GR-S 1500 or 1600 stock has another remarkable effect. GR-S stocks are characterized by the lack of tack. When these cyanoalkylated amines are added in amounts from 0.5 to 5 pts. per 100 pts. of polymer, the stock becomes tacky without being too soft for tire building. This property of tackifying GR-S stocks is an important characteristic of the cyanoalkylated polyarnines.

Table 3 IMPROVEMENT OF VULCANIZATION OF NON-ACIDIC CARBON BLACK ELASTOMER STOCKS BY CURING WITH CYANOALKYLATED MONO AND POLYAMINES Example No 3-1 3-2 3-3 Control Compound No., B- 17411 18480 18481 Poly-3-TEPA... 1 AgeRite Resin D 3 l 1 1 Zinc oxide 8 3 8 Circo Para 5 5 5 Santocure l 1 1 Sulfur 1. 75 1.75 1. 75 Mooney viscosity, Mil-4-- 69 63 66 Cure at 285 F., min... 120 90 Elongation, percent. 500 585 675 300% modulus, p.s 1, 970 1, 845 1, 505

5 Tensile, p.s.1 3, 530 3, 780 3, 625 Hardness 67 67 67 Heat build-up, F 86 65 68 Increase in tensile strength, percent. 7 3 Increase in elongation, percent. 17 15 1 G RS 1500 50 pts. Philblack O is equivalent to GR-S 1600.

2 Pnilblack O is a non-acid carbon black sold by Phillips Petroleum Company.

3 AgeRitc Resin D is the antioxidant polymerized trimcthyldihydroquino-line sold by R. 'I. Vanderbilt Company.

4 Circo Para is a mixture of 50 pts. of Circosol 2X11 from Sun Oil Company and 50 pts. oi Para Flux 2016 from C. P. Hall Company.

5 Santocure is N-cyclohexyl-ahenzothiazol sulfenamide sold by Monsanto Chemical Company.

'11 Table 3a Example No 321-2 Compound No., B- 421 19407 Elastorner and Filler:

GR-S 1600 75 GR-S 1500 100 50 Philblack O 25 Cyanoalkyl amine (Example No.): 5 DETA (2-5) 2 Stearic acid 1 1 Zinc oxide 1 t 3 3 AgeRite Resin D 1 1 Para Flux 2016 5 5 Santocure 5 1 1 A-32 0.20 0.20 Sulfur 2. 2. 5 Mooney viscosity, ML-4 44 41 Cure at 285 F., min 90 00 300% modulus, p.s.i 1, 250 515 Shore hardness 44 62 Tensile, p.s.i 2, 600 3, 510 Increase in tensile strength, percent NOTE.-FOI footnotes 1 through 5 see Table 3.

6 A-32 is a reaction product of butyraldehyde with butylidene aniline sold by Monsanto Chemical Company.

Table 4 shows that the cyanoalkylated monoand polyamines of this invention remarkably improve the tensile values of vulcanizates of non-acid non-polar vinylic filler, GR-S, stocks.

The N-cyanoalkyl-substituted monoamine increased the tensile value about 23%, while the cyanalkylated polyamine increased it 46%.

Table 4 IMPROVEMENT OF VULOANIZATION OF NON-ACID, NON- POLAR, VINYLIC FILLERJJLASTOMER STOCKS VJI'IH CYANOALKYLATED MONO- AND POLAMINES Example No 4-1 4-2 4-3 Compound No., B- 8443 18482 18483 Elastomer: GR-S 1500 100 100 100 Filler: S/DVB (90/10) 7 t 20 20 20 Cyanoalkyi amine (Example No.).

Mono-I-IP (1-1) 1 1oly-3-TEPA (2-10) l Zinc oxide 3 3 3 AgeRite Resin D 3 1 1 1 Steoric acid 1 l 1 Santocure 1 1 1 Sulfur 2. 5 2. 5 2. 5 Mooney, Mia-4.. u 50 45 47 Cure at 285 F 00 20 60 Elongation, percen 635 915 750 300% Modulus, p.s.i 400 105 340 Tensile, p.s.i 2,275 2, 725 3, 220 Hardness s 60 57 63 Heat build-up, 42 49 Increase in tensile strength, percent 19 41 Norm-For footnotes 3 and 5 see Table 3.

7 Colloidal sized emulsion copolymer of styrene-divinylbcnzenc, (90/10) combined with elastomer by cocoagulation.

Table 5 shows that elast-omers reinforced with polar vinylic fillers are improved by curing with cyanoalkylamines in accordance with the present invention. In the control, Example 5-1, and Example 5 2, employing carbonyl (ketone) vinylic filler, the cyanoalkylamines improved the tensile value In Examples 53 to 5-5 the carbonyl groups (aldehyde) were supplied by the methacroiein and acrolein components of the vinylic filler, which have substantially the same effect as when supplied by ketone components thereof. The N-tri-(propionitrile)- tetraethylene pentamine improved the tensile strength 34%, and these three examples, at 60 to 75 minutes cure (the last with more of the cyanoalkylamine) show the extremely flat nature of the cure obtained with the N-poly-a-cyanoaikylated polyamine, and that variations in the small quantity of the cyanoalkylamine used are not highly critical. Example 5-7, with its control 5-6, shows that with the active carbonyl groups supplied by acrolein in the vinylic filler, the addition of one part of the N-poly-alpha-cyanoalkylated polyamine produced a 46% increase in tensile strength.

12 Table 5 IMPROVEMENT OF VULOANIZAIION OF NON-AGIDIO,

POLAR VINYLIO FILLER, ELAS'I'OMER STOCKS BY OUR- ibwi gSITH OYANOALKYLATED MONO- AND POLY- Example No 5-3 5-4 5-5 5-6 5-7 Compound No., B- 17487 18402 18403 17486 17485 Elastomer (GR-S 1500) 100 100 100 100 100 100 100 Vinylic filler:

S/DVB/MIPK 20 20 S/DVB/M AC S/DVB/AG Cyanoalkylamine (Example No.):

Mono-poly 1-TEPA 8 1 Poly-poly 3-lEPA 1 1 2 1 Stearic acid". 1 1 1 1 1 1 1 AgeRite Resin 1 1 1 1 1 1 1 Zinc oxide 3 3 3 3 3 3 3 Santocure 1 1 1 1 1 1 ltax 1 Sulfur 2 5 2. 5 2. 5 2. 5 2. 5 2. 5 2. 5 Compound Mooney,

ML-4 58 81 54 64 71 55 62 Cure at 285 F., min 00 45 60 75 75 105 60 Elongation, percent 765 750 760 735 800 775 815 300% modulus, p.s.i 210 465 340 380 360 240 285 Tensile, psi 2, 365 3, 435 3, 280 3, 210 3, 260 1, 970 2,880 Hardness. 60 63 6 62 Tensile strength increase,

percent 45 46 NOTE.F01lOOtHOlJ6S 3 and 5 see Table 3.

Oolloidal sized emulsion copolymer of styrene/divinylbenzene/ methylisopropenyl ketone (70/10/20).

9 Colloidal sized emulsion copolymer of styrene/divinylbenzene/xnethacroiein (/10/10).

olloidal sized emulsion copolymer of styrene/divinylbcnzene/acrolein (80/10/10).

Altax is benzothiaryl disulfide sold by R. 'I. Vanderbilt 00., Inc.

Table 6 is submitted for comparison purposes. Cure of substantially the same stock with an unsubstituted amine, as disclosed in Burke application S.N. 378,735. filed September 8, 1953, efiects a marked improvement in tensile value, but the cure is sharply peaked. Furthermore, on storage of this compounded stock before curing, the benefit of the amine is partially lost, as shown (almost 760 psi. lower tensile strength being obtained). Likewise heat aging of the cured stocks initially containing the unsubstituted amine showed a considerable loss of tensile properties.

Table 6 SHARPLY PEAKED CURE OF ELASTOMER AND VINYLIC FILLER STOCK WITH A VOLATILE AMINE AND LOSS OF BENEFIT THROUGHOUT STORAGE Example No 6-1 6-2 Control Compound No., B- 2486 2430 Elastomer (GR-S 1500) 100 Vinylic filler: S/DVBIMAML, 20 20 Volatile amine (al1y1amine) 3 OaptaX 13 0. 5 Zinc oxide 5 3 Ethyl Tuads 0.15 Stearic acid 1 2 Altax 11 l Santocurc 5 1 25% 14-32 Mastcrbatch 0. 8 Sulfur 2. 5 2. 5 Compound Mooney, ML-4. 50 46 Cure* at 285F., min". 90 20 Elongation, Percent 815 815 300% modulus, p.s.i 375 Tensile, p.s.i 1,055 3, 725 Hardness. 50 46 *See the following table:

Cure, Psi. tensile Percent Herdmin. at strength along. S-300% ness 285 F 13 Table 6-Continued After compounding, storage for seven days before curing resulted in the following maxima Similarly 37 days storage prior to curing gave the following results Norm-For footnote 5 see Table 3, footnote 11 see Table 5.

12 Colloidal sized emulsion copolymer of styrene/divinylbenzcne/ methacrylic acid (80/10/10).

W 2-morcaptobonzothiazole.

H Tetraethylthiuramdisulfide.

1t A-32 (7) milled into GR-S 1500.

Table 7 shows that a variety of alpha-N-substituted propionitriles can be used as curing aids for GR-S 1500 reinforced with acidic vinylic fillers.

Shown are the results from the reaction products of 1 mol. lactonitrile with 1 mol diisopropyl amine (7-2) tert-butyl amine (7-3) tert-octyl amine (7-4) and allylamine (7-5). Increases of tensile strength from 153 to 182% are observed.

, Table 7 COMPARISON OF IMPROVEMENTS EFFECTED BY FOUR DIFFERENT a -CYANOALKYLATED MONO-AMINE IN SAME ELASTOllIER-ACID VINYLIC FILLER STOCK Example No 7-1 7-2 7-3 7-4 7-5 Control Compound No., B- 2486 2479 2480 2481 2478 Elastomer (GR-S 1500) 100 100 100 100 100 Vinylie filler: S/DVB/MAA (80/10/10) 12 20 20 20 20 .20 Cyl anoalkylamine (Example 0. 1-DIP (1-3) 5 1-TB (1-4) 4 1-TO (1-5) 1-AL (1-6)- 4 1 1 1 1 1 5 3 3 3 3 1 2 2 2 2 Santocurc 5 1 1 1 1 25 percent A-32 Masterbatch 15 0.8 0.8 0. 8 0. 8 Captax 13 0.5 Altax 1' Ethyl tuads 14 15 Sulfur 2. 2. 5 2. 5 2. 5 2. 5 Compound Mooney ML4 50 56 49 46 49 Cure at 285 F., min 90 90 90 -90 75 815 800 755 790 850 160 380 435 310 360 1, 055 2, 765 2, 980 2, 825 2, 670

percent 163 182 168 153 N0rE.For footnote 5 see Table 3, footnote 11, see Table 5, footn s 12, 13 14, and see Table 6.

17 Phenyl-beta-naphthylamine.

. Table 8 gives further examples of the improvement based on different specific cyanoalkyl-ated monoamines. It will be observed that in Examples 8-2 to 8-5 substantially the same increase of tensile strength was obtained as in Table 7, namely, in the range of 150% to 180% increase, and that in Example 86 in which the acid vinylic filler was cross-linked with tri-acrylylperhydro triazine, a tensile increase of 223% was obtained with the cyanoalkylated phenylarnine.

1 1 Table 8 IMPROVEMENT OF VULCANIZATION OF VINYLIC FILLER" ELASTOMER STOCKS BY CURING WITH VARIOUS MONO- CYANOALKYLATED MONOAMINES Cyanoalkylamine (Example No.):

2 .5 AgeRite Resin D 1 1 Zinc oxide 5 3 3 3 3 3 DPG: 0.5 Stearic acid. r 1 2 2 2 1 1 Altax 11 1 Santocure 5 1 1 1 1 1 11-32 24% Mastervatoh 0.8 0.8 0.8 Ethyl tuads 0.15 Sulfur 2. 5 2. 5 2. 5 2. 5 2. 5 2. 5 Mooney, ML-4 50 43 12 53 40 53 Cure at 285 F., min.-. 90 75 60 30 150 160 370 270 425 225 395 815 770 800 745 815 765 1, 055 2, 745 2, 740 2, 640 2, 960 3,370 5 6 66 Increase strength, percent 160 160 150 180 223 NorE.-For footnote 5 see Table 3, footnote 11 see Table 5, footnotes 11, 12, 14, and 15 see Table 6, footnote 17 see Table 7.

1s S/TAHT/MAA is a colloidal sized emulsion polymer of styrene/triacrylylhexahydrotriazine/metbacrylic acid (84/6/10).

DPG is diphenylquanidine, an accelerator.

In Table 8a four other examples are given for cyanoalkylated monoamines. These examples represent a group of amines in which the nitrogen is tri-substituted so that it is tertiary. All these cyanoalklated monoamines are effective in the vulcanization of acidic GRS 1500 stocks. Dicyanoalkylisopropyl amine (Example 8a-5) showed the highest increase in tensile strength (190%) over that of the control. The persubstituted ethanolamine (Example 8a-2) is the least effective from this group, although it increases the tensile strength 150% over the control.

Table 8a EFFECT OF MONO AND POLY-CYANOALKYLATED MON- OAMINES ON VULCANIZATION OF GR-S 1500 STOCKS CONTAINING ACID VINYLIC FILLERS Example No 8a-1 8a2 Sa-B 8a-4 8a-5 Compound No., B- 2486 19439 19440 19442 19443 Elastomer (GR-S 1500) 100 100 100 100 Vinylic filler:

S/DVB/MAA 12 20 20 2.0 20 S/DVB on S/MAH 20 Cyanoalkylamine (Example No.):

3-EA (144) 1 1-MD (1-15) 2-IPL (1-16) 2-IP (1-2). AgeRite Resin 1 1 1 1 Zinc oxide 5 3 3 3 3 Norm-For footnotes 3 and 5 see Table 3, footnote 11 see Table 5, footnotes 12, 13, and 14 see Table 6, footnote 27 see Table 13.

In Table 8b two examples are given for amines in which all the available hydrogens of the amino group are substituted with cyanoalkyl groups. A member of this group is represented in Example 85-2 by alpha-beta-beta- 15 16 tricyanoethylamine and in Example 8b-3 by tricyano- In Table 10 are compared tour substituted propiomethylalnine. Both are effective as curing aids. Trinitriles, namely beta, beta-iminobispropionitrile (1-2), cyanomethylamine tri-alpha-, alpha, beta-cyanopropylbeta-dimethylaminopropionitrile (103), beta-isopropylamine are less effective probably due to the presence of aminopropionitrile (1-4) and alpha-isopropylaminothe cyano groups close to the nitrogen, However, tensile propionitrile (-5).

strength increases up to 164% are observed. All four compounds are effective as curing aids for Table 8b acid GRS 1500 stocks with tensile strength increases of '120 to 160%. However, the outstanding properties of EFFECT OF TWO DIFFERENT POLYOYANOALKYLATED AMINES ON VULOANIZATION OF GR S 0 STOCKS CON; the alpha-substituted compound are demonstrated by the TAINING AOIDIG VINYLIO FILLERS 10 flat cure produced by the alpha-substituted propionitrile.

. Example NO 8M 81H From 45 to 105 minutes cure tune, the tensile values Control vary only from 2690 pan to 2845 p.s.l. W1th a hlgh of Compound No., B- 2486 19173 19495 19496 2965 at 60 minutes (Example 105). Especially remarkable are the tensile values after aging the cured El t GR-S 1500 100 100 100 100 vl iziib l lrz n samples at 212 F. for 48 hours. While the alpha-sub- $g7 n: ay-"55 stituted propionitrile still shows a tensile strength of Cyanoalkylamine p 2650 psi. those of the beta-substituted product are as (1-18 az-IBPN (1-19) Stearie acid A geRite Resin D low as 1755 psi.

Table 10a: In this table is demonstrated that the alpha, alpha-iml'no-bis-propionitrile can be used to advantage as a curing aid for acidic GRS 1500 stocks. Of the 4 substituted propionitriles described in Table 10, the beta, beta-imino-bis-propionitrile is a heretofore well known chemical compound per se. The di-alpha-substituted compound (Table 10a) seems to be more effective in the curing system, since only 1 part is suflicient to give the same increase in tensile strength as obtained with the 4 pts. of the corresponding beta-substituted compound. In both compounds the increase of tensile strength was N Ora-For footnote 3 see Table 3, footnotes 12, 13, and 14 see Table 6, footnote 19 see Table 8, footnote 23 see Table 13. 3

Table 9: The comparison of the curing rates of N-aminopropyl morpholine with its reaction product with 1 mol lactom'trile shows the advantage of the use of a 5 COMPARISON OF ALPHA AND BETA SUBSTITUTED cyanoalkyl product. the fI'C6 arnlne ShOWS a. sharp AMINO PROPIONITRILES AND THE ADVANTAGES 0F peaked cure with a maximum tensile strength of 2990 THE ALPHA-SUBSTITUTED PR PIO ITRILE p.s.i. at 60 minutes and 2350 psi. at 90 minutes (EX- ample 9-3) the cyanoalkylated amine gives a maximum tensile strength of 3100 psi. at the 60 minutes and the tensile values drop only to 2800 in the 90 minutes cure Compound (Example 9-2).

Table 10 Example No 10-2 10-3 10-4 l05 10-1 Control Table 9 Elastomer (GR-S 1500) 100 100 100 100 100 Vinylic filler (acidic): S/DVB/ COMPARISON OF THE CURE RATES FOR FREE AMINE MAA 2 2 2 20 AND CYANOALKYL-SUBSTITUTED AMINE Oyanoalkyl amlnes: Beta, beta-lmmobispropionltrile. 4 Example N 0 ig Beta dimethylaminopropioni- 4 trile Compound -l B 2486 12486 12487 Beta isop opylamjnopropionitrile 4 Elastomer (GR-S 1500 100 100 100 igg' fff?fi 11ft 4 Vinylic filler (acidic): Sl/DVB/MAA 20 20 20 Zinc oxide 5 3 3 3 3 Cyanoalkyl amine (Example No.): l-APM L0 1 1 2 2 2 2 Free amln N-ammopropy1morpho1lne 1 Santocures 1 1 1 Steam? -r 1 1 1 25% 11-32 Masterbatc 0.8 0. s 0.8 0.8 AgeRlte B85111 D 1 1 Sulfur 2. 5 2. 5 2. 5 2. 5 2. 5 PBNA (AgeRite Powder) 1 1 1 1 Z1110 oxlde- Ethyl tnads 0.15 Captex Capt-ax n 0, 5 511111001119- 34 Compound Mooney, ML-4. 50 49 50 50 53 E1 111111865 Cure at 285 F., min 75 75 75 75 Elongation, percent. 815 070 675 680 760 Mom, 1 300% modulus, .51. 402 354 378 359 Cure 111.285 F Tensile strength, p.s.i 1,055 2, 495 2, 300 2, 000 2, 705 1 t ,p r t Hardness 6 63 64 9 fi l Increase in tensile strength, percent 120 ens Properties after aging 48 hrs. at Har ness 0 R: Increase 111 19115116 Strength 194 182 Tensile strength, p,s,l 1, 070 2, 010 1, 755 2,650 Elongation, percent 490 480 565 Min. cure p.s.i. p.s.i. at 285 F. tens. 300% Elong. Hardness 65 Cure, B 2A33 B .2439 B 244() B 2441 min. at

285 El P 1 E1 l 1 El 60 3,100 810 250 64 Psi. Elong. P.s.i. 011g. .s. ong. .s.. 0mg. 75 2, 725 750 280 66 90 2, 800 735 285 57 950 150 2, 770 715 285 e7 2 850 a n a. a

N oral-For. footnote 3 see Table 3, footnote 11 see Table 5, footnotes 13 and 14 see Table 6. N01E.-For footnote 5 see Table 3, footnote 11 see Table 5, footnotes 1 Did not cure. 75 12, 13, and 14 see Table 6, footnote 17 see Table 7.

17 Table 10a 18 as shown in Examples 13-6 through 13-8. The optimum tensile values for the itaconic acid containing vinylic filler are between 3200 and 3460 p.s.i.

See footnotes at end of table.

Example No. 102-1 102-2 5 Table 11 COMPARISON OF THE EFFECT OF A OYANOALKYL Compound N0.,B- 2486 19496 SUBSTITUTED MONOAMINE IN GR-S 1500 STOCK 011 V VARYING AOIDITY AND DIFFERENT SOURCES OF THE OARBOXYL GROUPS Elastomer 100 100 5 255571111 5 20 E leN 11-1 11-2 1- 11 VT/DVB on 5 1553 11 20 10 Control 1 3 n 5 y a g g 81111118: p p -p 1 Compound No., B 18491 6471 6461 6470 6464 T1 T'l Zinc oxide 3 1111511 1 1 Elastomer (GR-S 1500) 100 100 100 Steenp acid 1 1 Source ofpolyaclcL s/MAE PAA PAA PAA S/MAH AgeR1te Resin D 1 Parts- 0. 756 1. 51 0.375 2 p 13 Philblnck 0" 25 25 25 25 25 Ethyl tuads 14 0-1 Cyanoalkyl amine,

DPG 25% MB 8 ample No.): l-IP 1-1)- 1 2 3 4 3 Sulfur. 2. 5 2. 5 AgeRite Resin D 3 1 Compound Mooney, ML-4 5 Zinc oxide 3 3 3 3 3 Cur at 111111- 9 90 Stearic acid 2 2 2 2 2 Elongation, percent- 815 690 Santocure 1 1 1 1 1 300% modulus, p.s.l. 160 70 A-32 0.2 0.2 0.2 0.2 Tensile, p.s.i 1,055 2,490 Sulfur 2.5 2.5 2.5 2.5 2,5 Hardness 67 Mooney, ML-4. 50 52 47 49 49 Increase in tensile strength, percent 1 Cure at 235 F, 6o 20 20 20 20 gloho lgatitzin,1 perce111 1 E35 323 (20 725 me 11 us .5. 80 2 20 680 Nor11.-For footnote 3 see Table 3, footnote 11 see Table 5, footnotes T g p 5 L32 3,100 3, 885 3, 700 3, 665 3, 700 12,13,2110 14 see Table 6, footnote 19 see Table 8, footnote 23 s TablelB. ardness 62 62 61 62 6o In t In Table 11 1s demonstrated that the efiectlveness of 25 551 52, 33 523}? 25 1g 18 19 the cyanoalkylated armnes 1s ne1ther dependent on the ggofig e at 212 for source of the carboxyl groups nor on their amoun s i T555115, p.s.i 2,075 2, 570 2, 430 2,550 the compounds. With increasing amounts of carboxyl Elongatiompercent- 380 groups, the amount of cyanoalkylated amine can be increased, h h amount i not very i i L AS NOTE.-FOI footnotes 2, 3, and 5 see Table 3, footnote 7 see Table 4. shown in Example 11-2 two parts of cyanoalkylated gf% xg e z anhydride p y amine give 3885 psi tensile strength at an acid content 0 y cry ac of 0.756 pt. of polyacrylic acid, while in Example 11-4 Table 12 four Parts Of cyarloalkylatedemine, at n a id content COMPARISON or MoNo-- AND POLY-CYANOALKYLATED of 0.375 pt. of polyacryhc acid yield a max1mum tensile POLYAMINE IN AN AOIDIO FILLER CONTAINING 1500 STOCK strength of 3665 p.s.1.

'In Table 12 are compared three cyanoalkylated poly- Example N0 1H 1H 1H 1H ammes 1n GR-S 1500 stocks contammg ac1d1c v1nyl1c c r fillers. One part of the cyanoalkylated amine is used in 40 Cmnpmmd 36 11405 11412 17451 each compound. 12-2 contains one mole of tetracthyl- 1 enepentamine reacted with one mole of lactonitrile, 12-3 ggffgfig gf fgg fi 100 the reaction product of one mole tetraethylenepentamine S/DVB/MAA 11 20 20 20 20 with two moles lactonitrile, and 12-4 represents the reiggggggg (Example N0): 20 action product of one mole of the same amine with 3 Mono-poly l-TEPA (2-8) 1 moles lactonitriles. The tensile strengths are practically gggjggg-gfifigigj fg f in the same range, between 3335 and 3500 p.s.i., which AgeRite Resin D 1 1 1 represents an increase from 215 to 230% over the tensile i f g fif 3 3 3 strength of the control. With the tri-substituted amine, s tearie 010- 1 1 the optimum tensile values are obtained at a slightly g f g; ":1: 1 longer curing time, which is not considered serious since EJ 1 171 tuads 14 faster curing rates may be obtained by the use of a slightye- 5; ly higher amount of the cyanoalkylated amine. 16 100110 1 11-4--- In Table 13 it is demonstrated that the same rnonoifi i percent cyanoalkylated amine can be efiectlve 1n 8 different 9 fi g ap Si GR-S 1500 stocks, containing acid vinylic fillers. The i eg H increases of tensile strength over that of the control lie 111016356111 tensile Strength, P810811 between 200 and 240% (Example 13-3). The bene- Nora-For footnotes 3 and 5 see Table 3, footnote 11 see Table 5 gil jf cgisg l gfi 8; footnotes 12, 13, and 14 see Table 6, footnote 18 see Table 8. 7 .S we y g p p 21 Durez 8-20092isaphenolresinfrom the Durez Plastiosand Chemical 1n the method of the preparation of the acld v1nyl1c filler Company, Inc.

Table 13 THE EFFECTIVENESS OF A MONO-CYANOALKYLATED POLYAMINE IN EIGHT DIFFERENT ACID STOCKS Example No 13- 1 13-2 13-3 13-4 13-5 13-6 13-7 13-8 13-9 on rol Compound No,, B- 2486 15480 15469 16342 16433 16434 16435 16466 14480 Elastomer (GR-S 1500) 100 100 100 100 100 100 100 100 Vinylic filler:

S/DVB/MAA 20 20 2o 1 1 1 1 1.5 1.5 1.5 1 Stearic acid", 1 1 1 1 l 1 l l 1 Table I3-C0ntinued THE EFFECTIVENESS OF A MONO-CYANOALKYLATED POLYAMINE IN EIGHT DIFFERENT ACID STOCKS Example N o 13-1 1 13-2 13-3 13-4 13-5 13-6 13-7 13-8 13-9 ontro Compound No., B- 2486 15480 15489 16342 16433 16434 16435 16436 14489 AgeRite Resin D 1 1 1 1 1 1 1 1 Altax 1 Zinc oxide 5 3 3 3 3 3 3 3 Captax O. 5 Santocure 1 1 l 1 1 1 1 1 Ethyl tuads 0.15 Sulfur 2. 5 2. 5 2. 5 2. 5 2.5 2. 5 2. 5 2. 5 2. 5 Mooney, ML-4 50 8 56 51 51 54 54 55 44 Cure at 285 F., min 90 75 90 30 30 75 75 75 30 Elongation, percent 815 760 785 765 800 800 760 765 725 300% modulus, p.s.i 160 270 450 340 345 275 300 300 370 Tensile, p.s.i 1, 055 3, 360 3, 570 3, 475 3,430 3, 370 3, 200 3,460 3, 515 Hardness e 50 67 69 67 65 64 61 64 64 Increase in tensile strength, percent 215 240 230 220 215 200 225 234 NOTE.-For footnotes 3 and 5 see Table 3, footnote 11 see Table 5, footnotes 12, 13, and 14 see Table 6, footnote 18 see Table 8. 23 Colloidal dispersion of copolymer oi vinyltoleune/divinylbenzene on styrene-maleic anhydride copolymer seed.

24 Colloidal dispersion of copolymer of styrene/divinylbenzene/itaconic acid 80/10/10 Santomersea'i 25 Colloidal dispersion of copolymer of styrene/divinylbenzenelitaconic acid 80/10/10 Triton 770.

Colloidal dispersion of copolymer of styrene/divinylbenzenelitaconic acid 80/10/10 Duponol ME.

11 Colloidal dispersion of copolymer of styrcne/divinylbenzene on styrene-maleic anhydricle copolymer seed.

Table 13 (Concluded) In Table 14 an example is given of the flat cure rate produced by the monocyanoalkylated polyamine. From 30 to 60 minutes the tensile values are practically constant between 3550 and 3590 p.s.i. At a 90 minute cure the tensile value drops only to 32.00 p.s.i., while hardness and elongation are substantially the same as for 30 to 60 minutes cure time.

Table 14 EXAll/IPLE FOR THE VERY FLAT CURE OF A MONOCYANO- A%(l)Kgl%ATED POLYAlVIINE IN AN AOIDIC GR-S 1500 S Example No 14-1 14-2 Control Compound N 0., B- 2486 11457 Elastomer (GR-S 1500) 100 100 Vinylic filler: S/DVB/l\1AA+BD/VP+resorcinol- CHZO 26 Cyanoalkylamine (Example N o.) -TEPA (2-8) 1 AgeRite Resin D 3 1 Zinc oxide 3 Stearic acid l Captax 13 1 Altax Monex 2B 0. 2 Ethyl Tuads 14 0. 1s

ulfur 2. 5 2 Compound Mooney, ML-4 5O 67 Elongation, percent i 815 775 300% modulus, p.s.' 160 375 3, 590 67 230 Cure, P.s.i. Percent .s.i. min. at tens. clong. 300% Hardness 285 F. 0d.

' NOTE.-F01 footnote 3 see Table 3, footnote 11sec Table 5, footnotes 13 and 14 see Table 6.

16 Colloidal sized emulsion oopolymer of styrene/divinylbenzene/ methacrylic acid (80/10/10) grafted with butadiene vinylpyridine (/5) and resorcinol-formaldehyde.

2B Monex is tetramethyl thiuram monosulfide sold by the N augatuck Chemical Division of the 11.8. Rubber Company.

Two examples (15-2 and 15-3) in Table 15 demonstrate that the effectiveness of a polyamine as a curing aid for GR-S 1500, containing an acid vinylic filler is not influenced significantly by an increase in the number of cyanoalkyl groups from one to two.

2950 and 2835 are shown as maximum tensile values. Considering the higher molecular weight of the cyanoalkylated polyamine in Example 15-3, and the fact that in both compounds the same amount (1 part) is used, the efiectiveness of the high substituted polyamine can be raised by the use of slightly higher amounts.

Table 15 EFFECT OF MONO- AND DI-CYANOALKYLATED POLYAMINE IN SAME ACID STOCK Example N o 15-1 Control 2486 Compound No., B- 7435 NOEL-For footnotes 3 and 5 see Table 3, footnote 11 see Table 5, footnotes 12, 13, and 14 see Table 6.

In Table 16 the cyano'alkylation reaction is not limited to the pure distilled polyamines. The Example 16-2, a reaction product of one lactonitrile with the mixed polyamines remaining as residue from the distillation of tetraethylene pentamine was employed, While in 16-3 the reaction product with four lactonitriles was used. Both are effective as curing aids in an acid GR-S 1500* stock. Tensile values as high as 3240 p.s.i. are found in EX- ample 16-2. As a further example for the flatness of the cure produced by the cyanoalkylated polyamine, all four cures are given for Examples 16-2 and 16-3. Over a range from 30 to min., the tensile values change only from 3010 to 3240 p.s.i. in Example 16-2.

Table.16

EFFECT OF MONO- AND POLY-CYANOALKYLATED MIXED POLYAMINES IN SAME ACID GR-S 1500 STOCK Example No 16-1 16-2 16-3 Control Compound No., B- i- 2486 12484 12485 Elastomer (GR-S 1500) a 100 100 100 Vinylic filler: S/DVB/MA 20 20 20 Cyanoalkylamine (Example l-MPAD (2-12). 1 4-MPAD (2-13) Stearic acid AgeRite Resin D Santoeure Ethyl tuads Mooney, ML-4 50 Cure at 285 F m1n 90 Elongation, percent 815 750 785 300 percent modulus, p.s.i- 160 335 275 Tensile, p.s.i. 1, 055 3, 240 2, 780

Hardness l 50 Increase in tensile strength, percent 205 160 Cure, p.s.i. Percent 300% Hardmin. at tens. elong mod., ness 285 F. p.s.i

No'rn.F0r footnotes 3 and 5 see Table 3, footnote 11 see Table 5, footnotes 12, 13, and 14 see Table 6.

In Table 16 it was shown that cyanoalkylated mixed polyamines from distillation residues can be used successfully as compounding ingredients. In Table 17 two other examples are given for monoand tetracyanoalkylated mixed polyamine residues of different sources. In Example 17-2 tensile values as high as 3490 p.s.i. can be obtained by the use of only one part of the cyanoalkylated polyamine.

Table 17 EFFECT ON VULCANIZATION OF MONO- AND POLY- CYANOALKYLATED MIXED POLYAMINES IN DIFFER- ENT ACID GR-S 1500 STOCKS Example No 17-1 17-2 17-3 Control Compound No., B- 2486 16460 9-197 Elastomer (GR-S 1500) 100 100 100 Vinylic filler:

VT/DVB on S/MAH 13 n 20 S/DVB/MAA .e 20 20 Cyanoalkylamine (Example No.).

l-MPAH 11) 1 4-MPAC (2-31) 1 Stearie acid 1 1 1 AgeRite Resin D 1 1 Altax 11 e e e, 1 Zinc Oxide. 5 3 3 Oaptax L 0. 5 Santocure 1 1 Ethyl tuads 0.15 Sulfur 2. 5 2. 5 2. 5 Mooney, ML-4- 50 43 Cure at 285I*., 111111 90 20 90 Elongation, percent 815 875 760 300% modulus, p,s.i 160 225 280 Tensile, p.s. 1,055 3, 490 2, 925 Hardness. 50 6 63 Increase in tensile strength, percent 230 175 Nora-For footnotes 3 and 5 see Table 3, footnote 11 see $1161; 5 footnotes 12, 13, and 14: see Table 6, footnote 23 see Table 18 EFFECT OF MONO- AND POLY-CYANOALKYL-ATED POLY- AMINE ON VULCANIZA'IION OF ACID GR-S 1500 STOCK Example No 18-1 18-2 18-3 Control Compound No., B-. 2486 10445 10446 Elastomer (GR-S 1500) 100 100 Vinylie filler: S/DVB/MAA 20 20 20 Cyanoalkylarm'ne (Example N0 I-IBPA (2-14) 1 2-IBPA (2-15) 1 AgeRite Resin D 3 1 l Zinc oxide 5 3 3 Altax 11 1 Stearie acid 1 1 1 Captax 13 0.5 Santocure 5 1 1 Ethyl tuads 0.15 Sulfur 2. 5 2. 5 2. 5 Mooney, ML-4- 50 63 45 Cure at 285 F., mm. 90 90 Elongation, percent 815 725 765 300% Modulus, p. 430 330 Tensile, p.s.i- 1, 055 2, 850 3, 065 Hardness 50 63 63 Increase in tensile strength, pereent N O'lE.-F0r footnotes 3 and 5 see Table 3, footnote 11 see Table 5, footnotes 12, 13, and 14 see Table 6.

Five examples are given in Table 19 for a cyanoalkylated polyamine. Diethylene triarnine was progressively cyanoalkylated from one to five cyanoalkyl groups in the molecule. From each compound only one part was used in the compounding recipe. Increasing tensile strength starting from the 2875 p.s.i. in 19-2 up to 3440 p.s.i. in 19-6 is observed. Due to the higher molecular weight of the three to five substituted polyamine and the therefore slower reaction rate, the amount of accelorator (Santocure) Was raised from 1 to 1.5 parts to obtain comparable rates of vulcanization.

Table 19 EFFECT OF SUBSEQUENT N-SUBSTIIUTION OF POLY- AMINE WITH A CYANOALKYL ON VULCANIZATION PROPERTIES IN ACID GR-S 1500 STOCK Example No 19-1 Control 2486 Compound No., B

Elastomer (GR-S 1500) Vinylie filler: S/DVB/MAA 1-DETA (2-1) Z-DEIA (2-2) 3-DEIA (2-3) e-DETA (2-4) 5-DETA (2-5) Stearie acid AgeRite Resin D 3 Zine oxide Captax Santocure 5 Ethyl tuads Increase in tensile strength,

percent Norm-For footnotes 3 and 5 see Table 3, footnote 11 see Table 5, footnotes 12, 13, and 14 see Table 6.

In Table 20 are given two examples for a polyamine aoeeeee Table 20 EFFECT OF MONO- AND POLY-CYANOALKYLATED POLYAMINES HAVING TVJO OXYGEN IN THE CHAIN VULCANIZATION OF AN ACID GRS 1500 Example No 20-1 20-2 20-3 Control Compound N 0., B- 2486 18487 18488 1 2-EBOP (2-17) 1 Stearie acid 1 AgeRite Resin D 1 1 Zinc oxide 5 3 3 Captax 0.5 Santocure L 1. 5 1. 5 Ethyl tuads 0.15 Altax 1 Sulfur 1 2. 5 2. 5 2. 5 Mooney, ML4 50 55 Cure at 285 F m1n 90 9O 60 Elongation, percent 815 675 710 300% modulus, p s 160 540 400 Tensile, p.s.i. 1,055 3, 510 3,000 Hardness 50 68 66 Increase in tensile strength, percent 230 185 NOTE.-F01 footnotes 3 and 5 see Table 3, footnote 11 see Table 5, footnotes 12, 13, and 14 see Table 6.

In Table 21 is shown the use of a diand tetra-cyanoalkylated diamine with a straight hydrocarbon chain. 160% increase over the control was gained in tensile strength in comparison with the control.

In Table 22 it is demonstrated that the efiectiveness of a polycyanoalkylated polyamine in the curing of an acidic GR-S 1500 stock is not limited to a specific compounding recipe. One part of the substituted polyamine is used in six different acceleration systems. Slight variations in the tensile values (from 2970 to 3380) are observed, and doubtless these values can be adjusted by using slightly different amounts of the accelerators. It is demonstrated in all six compounding formulae, the cyanoalkylated polyamine shows its eifectiveness.

In Table 23: In the presence of cyanoalkylated monoand polyamines, zinc oxide and stearic acid dissolve readily upon heating to about 130-140 C. and form clear transparent solutions. After cooling more or less hard wax-like products are formed which can be handled very easily. In Table 23 are given some examples for these materials and their effectiveness in the vulcanization of acidic GR-S 1500 stocks is demonstrated by six examples. The cyanoalkylation of the polyamine can be carried out while heating the amine with the zinc oxide and the stearic acid. In this case some water has to be evaporated. Other additives such as tall oil or petrolatum can be admixed (Example 23-2). The effect of these compounded cyano alkylated amines is of the same order as for the free cyanoalkylated amines.

In Table 23a: The reaction products of a cyanoalkylpenta-substituted polyamine (1 mole) with zinc oxide /2 mole) and stearic acid (1 mole) (Example #23a-2) and the reaction product of the tricyanoalkylated polyby heating. When these materials are incorporated in acidic GR-S 1500 stocks, they act as very good curing aids as demonstrated by this table. Tensile values of 3000 psi. are obtained, which represent an increase of more than 180% over the control.

Table 2] EFFECT OF POLY-CYANOALKYLATED DIAMINE, HAV- ING SIX CARBON BETWEEN THE NITROGEN ATOMS, ON THE VULCANIZATION OF AN ACID GR-S STOCK Example No Compound No., B-

21-1 Control 2436 Elastonler (GR-S 1500) Vinylic filler: S/DVB/MAA Cyanoalkyl-amine (Example N o.

2-HMDA (2-18) 4-HMDA (2-19) Stearic acid Zinc ox1de Captax Santocure Mooney, 50 57 52 Cure at 285 F., 90 90 Elongation percent 815 755 740 300% modulus p.s. 335 400 Tensile, psi 1, 055 2, 770 2, 750 Hardness. 50 67 67 Increase in 163 161 N0'rn.For footnotes 3 and 5 see Table 3, footnote 11 see Table 5, footnotes 12, 13, and 14 see Table 6.

Table 22 EFFECTIVENESS OF A POLY-CYANOALKYLATED POLY- AMINE IN SIX DIFFERENT COMPOUNDING RECIPES FOR AN ACID GR-S 1500 STOCK Oyauoalkyl-amine Accelerator 808 31 Trimene base 32 Sulfur Ethyl tuads Increase in tens strength, percent.

NOTE.FOr footnote 3 see Table 3, footnote 11 see Table 5, footnotes 12, 13, and 14 see Table 6, footnotes 18 and 19 see Table 8, footnote 28 see Table 14.

Diorthotolylguanidine sold by DuPont de Nemours Co.

30 Copper dialkyldithiocarbamate sold by R. T. Vanderbilt.

31 Condensation product of butyraldehyde and aniline sold by E. I. duIont de Nemours & Co., Inc.

32 A reaction product of ethylchloride, formaldehyde and ammonia sold by N augatuck Chemical Division of US. Rubber Co.

EFFECT OF OOMPOUNDED CYANOALKYLATED AMINES ON VULGANIZATION OF ACID GR-S STOCKS Example No 23-1 23-2 23-3 23-5 23-6 23-7 Control Compound N 0., B 2486 10469 10470 10416 10417 10418 9496 Elastomer (GR-S 1500) 100 100 100 100 100 100 100 Vmyhc filler: S/DVB/MAA 12 20 20 20 20 20 2o 20 Oyanoalkyl amine composition:

11 g. allylaminopropionitrile, 28 g. stearic acid, 4 g. ZnO 4 8 g. ZnO, 28 g. tall oil, 28 g. stearic acid, 20 g. petrolatum 2295,

9 g. polyamine H, 9 g. polyamine T, 14 g. laotonitrile 4 29Zg.(yanoalky1ated polyamine (2-11), 28 g. stearic acid, 4 g.

n 2 237g. C ):yanoalkylated polyarnine (2-11), 28 g. stearic acid, 4 g.

23Zg.(r):yanoalkylated polyamine (an), 56 g. stearie aeicif'i' 20 g. 2-TEPA (2-9), 28 g. stearic acid, 4 g. ZnO- Stearrc acid- AgeRite Resin D 3 Captax 13 Santocure Ethyl tuads 14 Altax 11 1 Sulfur 2. 5 2. 5 2. 5 2. 5 2. 5 2. 5 2. 5 Mooney, ML-4 50 37 40 44 44 44 44 Cure at 285 F., min.-- 90 9O 90 30 45 45 45 Elongation, percent 815 700 715 1, 000 785 825 740 Modulus, 300% 160 370 335 210 325 285 280 Tensile, p.s.1 1, 055 2, 975 2, 860 2, 885 3, 085 3, 150 3,000 Har 5 67 57 6 64 63 Nora-For footnotes 3 and 5 see Table 3, footnote 11 see Table 5, footnotes 12, 13, and 14 see Table 6.

Table 23a EFFECT OF RESINOUS CYANOALKYLATED POLY- AMINES 0N VULCANIZATION OF ACID GR-S STOCKS Example No 23a-1 23a-2 23a3 Control Compound No., B- 2486 19475 19476 Elastomer (GR-S 1500) 100 100 100 Vinylic filler:

S/DVB/MAA (8O/10/10) 20 VT/DVB (95/5) on 10 S/MA 2O Cyanoalkylamine (Example No.):

5DETA-S* 2 3-DEIA-S** 2 PBNA 17 l l l Stearic acid 1 1 1 Zinc oxide- 5 3 3 Altax 1 1 1 Captax 0.5 Ethyl tuads 14 0.15 DPG 0.2 0. 2 Sulfur 2. 5 2. 5 2. 5 Mooney, ML-4... 50 48 47 Cure at 285F., min 90 60 Elongation, percent.-. 815 835 660 300% modulus, p s 1 160 330 585 Tensile, p.s r... 1,055 3,005 3,015 Hardness 50 68 Increase in tensile strength, percent"- 185 186 *1 mole 5-DETA (2-5), 1 mole stearic acid and A mole Zoo.

1 mole 3-DETA(23), 1 mole stearic acid and V mole ZnO.

Norm-For footnote 11 see Table 5, footnotes 12,13, and 14 see Table 6, footnote 17 see Table 7, footnote 19 see Table 8, footnote see Table 24.

When polyoyanoalkyl polyamines are heated with small amounts of metal oxides or metal salts above 100 C., an exothermic reaction is initiated which is accompanied with an appreciable rise of temperature, depending on the nature of the salt or oxide. The reaction products are dark brown, very hard resinous materials with softening points of 100 C. and above.

For increased processibility of these resinous products (for instance, for the incorporation in elastomers on the, mill) these resins can be plasticized with fatty acids, tall oil, mineral oils and the like.

These materials are hard and brittle at room temperature and the softening points are below 80 C. when plasticized.

Metal oxides, capable of initiating the reaction are for example: Zinc oxide, cadmium oxide, calcium oxide, magnesium oxide, lead mono and dioxide, stannous and stannic oxide, etc.

Salts capable of performing the resinification reaction are for instance: Zinc stear-ate, cobalt naphthenate, manganese naphthenate, and the like.

Example I.-36.8 g. S-DETA (Table 2-5) are heated with 28 g. of stearic acid and 4 g. of zinc oxide. At 135 C. a violent reaction is initiated which causes the temperature to raise up to 195 C., forming a dark brown clear solution. The reaction product is hard and brittle at room temperature and has a softening point below C.

Example II.33.1 g. 4-HMDA (Table 2-19) are heated with 28 g. stearic acid and 4 g. zinc oxide. A violent re action is initiated at C. causing a temperature rise to C. A clear dark brown solution is formed. The cold material is hard and brittle and the softening point is below 80 C.

Example III.--36.8 g. S-DETA (Table 2-5) are heated with 32 g. zinc stearate. The zinc stearate dissolves at 150 C. readily in the cyanoalkyl amine and initiates a violent reaction, causing a temperature rise to C. The resinous reaction product is hard and brittle at room temperature and has a softening point below 80 C.

The chemical structure of the cyanoalkyl group has some influence on the effectiveness of the substituted polyamine. In Table 24 four examples are given for cyanoalkylated polyamines and in Table 24a three examples of cyanomethyl polyethyleneamines are shown. -In Example 24-2 and 24-3 the cyanoalkyl group is alpha-methylpropionitrile, in Example 24-4 it is alpha-phenylpropionitrile, and in 24-5 it is alpha-isopropenylpropionitrile and in 24a-2 and -3 the additives contain cyanomethyl groups. The highest tensile values are shown by the latter with 3055. However, the other cyanoalkylated polyamines of Tables 24 and 24a increased the tensile strengths from 135 to 181% above that of the control.

Table 24 EFFECTIVENESS OF CYANOALKYLATED POLYAMINES,

(HEREIN CYANOALKYL IS OTHER THAN PROPIONI- TRILE.

ON VULCANIZATION OF ACIDIC GR-S 1500 See footnotes at end of table.

Table 24Cont1nucd Table 25C0mmued Example No 24-1 24-2 24-3 24-3 24-5 Cure, p.s.i. Percent 300% Hard- Gontrol min at tens. elong. mod, ness Compound No., B 2486 9464 9465 19441 10445 7 285 F p.s i

AgeRite Resin D 3 Example 25-1 (B-15435)- 30 2, 670 490 1, 835 80 Zinc oxide 60 3, 400 475 2, 425 82 Stearic acid. 75 3, 225 415 2, 500 81 Altax 11 90 3, 330 350 2, 605 82 Oaptax 13 Example 25-2 (B-15436) 30 3, 465 400 2, 860 82 Santocure 5 w 60 3, 840 350 3, 060 82 Ethyl tuads 1 9o 4, 015 375 3, 180 sa Sulfur 120 3, 775 350 3, 155 83 Llooney, ML-4. Example 25-3 (Ii-15437) 30 3, 200 590 1, 595 73 Cure at 285 F., min. 60 3, 530 510 2,015 73 Elongation, percent. 75 3, 515 490 2, 045 74 300% modulus, p.s. 90 3, 660 475 3, 315 76 Tensile, p.s.i- Hardness. 68 68 72 67 15 Increase in tens 135 160 145 190 Nora-For footnote 11 see Table 5.

Norm-For footnotes 3 and 5 see Table 3, footnote 11 see Table 5, footnotes 12, 13, and 14 see Table 6.

85 Copolymer of vinyl toluene and divinylbenzene (95/5) in presence of pts. styrenemaleic anhydride copolymer.

Table 24a EFFECTIVENESS OF CYANOALKYLATED POLYAMINES,

WHEREIN CYANOALKYL IS OTHER THAN PROPIONI- TRILE, ON VULCANIZATION OF AOIDIO GR-S 1500 STOCKS Example No 24a-l 24a-2 24a-3 Control Compound N 0., B- 2486 19474 19477 Elastomer (GR-S 1500) 100 100 100 V inyllo filler:

S/DVB/MAA (80/10/l0) VT/DVB on 10 S/MAH-.. 20 2O Cyanoalkylamine (Example No 2G-TEPA (2-35 1 fiG-DETA (2 36) 1 PBN 1 Stearic acid. 1 1 1 AgeRite Resin D 1 1 Zinc oxide 6 3 3 Altax 1 1 1 Captax 13 0.5 Ethyl tuads 14 0. 15 DPG 19 0.2 0.2 Sulfur 2. 5 2. 5 2. 5 Compound Mooney, ML-4. 51 49 Cure at 285 F., min 90 90 Elongation, percent 815 690 775 300 percent modulus, p.s.i 160 490 400 Tensile, p.s.i. 1, 055 2, 925 2, 960 Hardness- 6. 64 Increase in tensile strength, percent 178 181 Norm-For footnote 3 see Table 3, footnote 11 see Table 5, footnotes 12, 13, and 14 see Table 6, footnote 17 see Table 7, footnote 19 sec Table 8, footnote 35 see Table 24.

The data of Table 25 demonstrate that the cyanoalkyl-ated amines are effective in grafted GR-S 1500' stocks containing, e.g., polyacrylic acid as well as in GR-S 1500 stocks containing a polyacid. Tensile strengths up to 4015 p.s.i. were obtained in Example 25-2 and an excellent flat cure is demonstrated by the values for four differcnt cure times. The comparison of Examples 25-1 and 25-3 shows that besides the improved tensile values 400 p.s.i. vs. 3660 an improvement of the 300% modulus could be achieved (from 2425 to 3315 p.s.i.).

Table 25 EFFECT OF CYANOALKYLATED POLYAMINE IN TWO DIFFERENT LEVELS ON VULCANIZATION OF GRAFT- ED ACID GR-S 1500 STOCKS See footnote at end of table.

a of a copolymcr of MAA/DVB/S (27.4).

Table 26 demonstrates that the cyanolkylated monoamine is effective in curing GR-S 1500 stocks containing an acid vinylic filler and a polyacid, together with carbon block. In Example 26-2 a high tensile strength of 3900 p.s.i. was obtained with 10 pts. of an acidic vinylic filler and 27 pts. of carbon black, Whereas the hardness of the cured stock did not exceed 72.

Table 27: In this table it is shown that the cyanoalkylatcd polyamine is effective in the vulcanization of a GR-S 1500 stock containing entirely diiferent types of polyacids together with 25 parts of carbon black. The substituted polyarnine is a powerful curing aid for the carboxyl groups supplied by 2 pts. polyacrylic acid (Example 27- 2) as well as for the carboxyl group supplied by 2 pts. of pectic acid or by a copolymeric acid (12.5 pts.) consisting The highest tensile value (3850 p.s.i.) was obtained in Example 27-2 containing polymethacrylic acid.

Table 27a: The same polycyanoalkylated polyaminc is shown in two different concentrations in two acidic GR-S 1500 stocks. As seen in Example 27a-2 a small amount (e.g., 0.5 pt. per hundred parts of polymer) of dicyanoalkyldiethylcnetriamine was very effective. The tensile strength was 330 p.s.i. above that of the control. In Example 2711-3 where 1.5 pts. of cyanoalkylated amine were used to correspond to the higher amount of carboxyl groups (4 pts. of S/MAH copolymer) present in the GR-S 1500, a tensile strength of 3600 p.s.i. was obtained.

Table 26 EFFECT OF GYANOALKYLATED MONOAMINE IN GR-S %%(IJJ%CQI)NTAINING AOIDIO VINYLIO FILLER AND Example No 26-1 26-2 26-3 Control Compound No., B- 2486 6491 5488 Elastomcr (GR-S 1500) 100 100 Vinylic filler:

S/DVB/MAA 20 10 5 Polyacrylic acid. 2 HAF black 27 36 Cyanoalkyl amine (Example N 0.): l-IP (1-1) 0. 5 1. 0 AgeRite Resin D 3 1 Zinc oxide 5 3 3 Ethyl tuads O. 15 Stearic acid. 1 1 2 A1116}; 1 2 Santocure 1' 1 Captax 0.5 Sulfur 2. 5 2. 5 l. 9 Mooney, ML-4 50 62 62 Cure at 285F., min 90 75 90 Elongation, percent- 815 620 580 300% modulus, p.s.i.- 1,280 1, 625 Tensile, p.s.i c 1,055 3, 900 3,270 Hardness 50 72 70 NOTE.FO1 footnotes 3 and 5 see Table 3, footnote 11 see Table 5, footnotes 12, 13, and 14 see Table 6.

MOO-CARBON BLACK STOCK INDEPENDENT OF CHEM- ICAL NATURE OF ACID ADDITIVES Example No 27-1 27-2 27-3 27-4 Control Compound No., B- 18491 6493 6495 7423 Elestomer (GR-S 1500) Source of acidity:

S/MAH PMAA 21 Pectic acid Philblack O 25 25 25 25 Cyanoalkyl amine (Example N 0.): 1-

TEPA (2-8) 0.5 0.5 0.5

AgeRite Resin D. 1 1 1 1 Zinc oxide 3 3 3 3 Stearic acid- 2 2 2 2 Santocure.-- 1 1 1 1 Suliur 2 5 2 5 2. 5 2 5 Mooney, ML-4 50 51 54 51 Cure at 285F m 60 45 45 300% modulus, p s 1- 1, 360 860 1, 220 825 Elongation, percent- 480 690 590 650 Tensile, p.s.i-. 3,100 3, 850 3, 650 3, 725 Hardness 63 62 67 65 Increase in tensile strength, percent 24 17 20 Properties at 212F.:

Tensile, p.s.i 1,020 1, 200 1,030

Elongation, percent 310 310 330 NOTE.FO1I00tI10te 20 see Table 11, footnote 23 see Table 13. [D A copolymer of malelc anhydride divinylbenzene and styrene (1/0.1

Table 27a EFFECT OF CYANOALKYLATED POLYAMINE IN TWO and maleic anhydride.

Tables 28 through 33: Examples are given to demon- :strate that the cyanoalkylated amines can be used as curing aids for GR-S compounds containing fillers other than I-IAF carbon black (Philblack O) together with a polyacid. In all cases an improvement of tensile strength can be observed when the curing aids of this invention (in combination with the polyacids) are presout. The carbon black controls in Tables 28, 29 and 30 are compounded Without containing a polyacid. To demonstrate that the improvement in tensile strength is due to the use of the cyanoalkylated amine and not due to the presence of the polyacid alone, in Table 33 the tensile values for GR-S 1500 compounded with (a) Philblack 0 alone, (b) With Philblack O and polyacid,

and (c) with a polyacid-cyanoalkylated amine combination, are compared. In Example 33-1 wherein two However when 3 parts of a cyanoalkylated monoamine DIFFERENT LOADS ON VULOANIZATION OF ACIDIC GR-S 1500 STOCK Example No 27a-1 2721-2 2721-3 Control Compound No., B- 18491 6479 6480 35 Elastomer (GR-S 1500) 100 100 100 Acid copolymer (S/MAH 4 Acid copolymer (MAA/MAH 1 Philblack 0 25 25 25 4O Cyanoalkyl amine: 2-DETA (2- 0. 5 1. 5 AgeRite Resin D 3 1 1 1 Zinc oxide 3 3 3 Stearic acid 2 2 2 Santocure 1 1 1 Sulfur 2. 5 2 2 Mooney, ML-4 50 48 48 Cure at 285 F., mm so 105 so Elongation, percent- 480 640 800 300% modulus, p.s.i- 1, 360 775 670 Tensile, p.s.i 3, 100 3, 430 3, 600 Hardne s 63 62 61 Increase in tensile strength, percent 10 16 Properties at 212 F.:

Tensile, p s i 1,000 1,080 Elongation, percent 365 495 50 30 are added as demonstrated in Example 33-3 the tensile strength increases to 3700 p.s.i.

In Table 34 is demonstrated the effectiveness of two different cyanoalkylated amines in the vulcanization of an acid terpolymer of butadiene, styrene and methacrylic acid. The tensile values are more or less in the same range, however, as similarly demonstrated in Examples 3-2 and 3-3 (Table 3), the elongation at maximum tensile strength is remarkably improved (28% in Example 34-2).

Table 35: Cyanoalkylated amine can also be used for curing neoprene containing acidic vinylic fillers. Acidic vinylic fillers retard the cure and sometimes even make it impossible to obtain acceptable proper-ties of the vulcanizate; the presence of the cyanoalkylated amine in Examples 35-2 and 33-3 resulted in the same cure time as in the control 35-1.

Table 28 EFFECT OF MONO-CYANOALKYLATED POLYAMINE IN CURING OF GR-S 1500 STOCKS CONTAINING OTHER FILLER THAN VINYLIC FILLERS OR PHILBLACK 0" [Furncx black reinforced GR-S 1500] Example No 28-1 28-2 Compound No., G- 3912 4107 Elastomer (GR-S 1500) 100 Polymethacrylic acid 21 1 Furnex. 35 35 Oyanoalkyl amine (Example No.): 1-TEPA (2-8)- 0.5 AgeRite Resin D 3 1. 0 1. 0 Circosol 2XH 2. 5 2. 5 Para Flux 2016 4 2. 5 2. 5 Zinc oxide 3. 0 3. 0 Stearic acid 1. 0 1. 0 Santocure 5 1.0 1.0 Suliur 2. 5 2. 5 Mooney, ML-4 43 44 Cure at 285 F., min. 60 30 Elongation, percent 810 780 300% modulus, p.s.i 470 550 Tensile, p.s.i- 2,310 2, 680 Hardness.-. 49 53 Increase in tensile strength, percent 16 Properties at 212 F.:

Tensile, p.s.i 650 730 Elongation, percent 350 435 Norn.For footnotes 3, 4, and 5 see Table 3, footnote 21 see Table 11.

Table 29 EFFECT OF MONO-CYANOALKYLATED POLYAMINE IN CURING OF GR-S 1500 STOCKS CONTAINING OTHER FILLER THAN VINYLIC FILLERS OR PHILBLACK O [Micronex W-G reinforced GR-S 1500] Example No 20-1 29-2 Compound No., G- 3901 3895 Elastomer (GR-S 1500) 100 100 Polymethacrylic acid 21 1 Micronex W-G 2 25 Oyanoalkyl amine (Ex 0. 5 AgeRite Resin D l 1 Circosol 2X13 4 2. 5 2. 5 Para Flux 2016 4 2. 5 2. 5 Zinc oxide 3 3,0 Stearic acid 1 1 Santocure 5 1 1 Sulfur .5 2. 5 Mooney, ML-t 45 Cure at 285 F., min 20 885 250 3, 210 50 Increase in tensile strength, perce 8 Properties at 212 F.:

Tensile, p.s.i 560 620 Elongation, percent 400 500 NoTn.For footnotes 3, 4, and 5 see 31 Table 30 EFFECT OF MONO-CYANOALKYLATED POLYAMINE IN CURING OF GR-S 1500 STOCKS CONTAINING OTHER FILLER THAN VINYLIC FILLERS OR PHILBLACK O [Dixie clay reinforced GR-S 1500] Example N 301 30-2 Compound No., G- 3893 3892 Elastomer (GR-S 1500) 100 Polymethacryllc acid 1 Dixie clay 72 Oyanoalkyl amine (Example No.): 1-TEPA (2-8). 0.5 AgeRite Resin D 3 1 1 Circos012XH 2. 5 2. 5 Para Flux 2016 4 2. 5 2. 5 Zinc oxide 3 3 Stearic acid 1 1 Santocure 5 1 1 Sulfur .1 2. 5 2. 5 Mooney, ML-4 50 48 Cure at 285 F., min. 120 45 Elongation, percent- 780 810 300% modulus, p.s.i 450 180 Tensile, p.s.i- 1, 980 2, 420 Hardness 5 57 Increase in tensile strength, percent- 22 Properties at 212 F.:

Tensile, p.s.1 470 570 Elongation, percent 470 495 Nora-For footnotes 3, 4, and 5 see Table 3, footnote 21 see Table 11.

Table 3] LER THAN VINYLIC FILLERS OR PHILBLACK O [Sllene EF reinforced GR-S 1500] Example No 31-1 31-2 Elastomer (GR-S 1500) 100 100 Polymethaerylie acid 1 Silene EF 57 57 Cyanoalkyl amine (Exam le No TE PA (28) 0. 5 AgeRite Resin D 3 1 1 Circoso12XH 2. 5 2. 5 Para Flux 2016 2. 5 2. 5 Zinc n i 3 3 Stcaric acid. 1 1 Santocure 1 1 Sulfur 2. 5 2. 5 Mooney, ML-4 93. 5 84 Cure at 285 17., min 60 Elongation, percent 770 810 300% modulus, p.s.i 370 420 Tensile, p.s.i 1, 800 2, 010 Hardne 61 00 Increase in tensile strength, percent 12 Properties at 212 F.:

Tensile, p.s.i 490 670 Elongation, percent 370 545 Nora-For footnotes 3, 4, and 5 see Table 3, footnote 21 see Table 11.

Table 32 EFFECT OF lVIONO-CYANOALKYLATED POLYAMINE IN CURING OF CR-S 1500 STOCKS CONTAINING OTHER FILLER THAN VINYLIC FILLERS OR PHILBLACK 0 [Hi Sil reinforced GR-S 1500] Example No 1. 321 32-2 Compound No., G- 3896 3890 Elastomer (GR-S 1500) 100 100 Polymethacrylic acid 1 Hi Sil 1 54 54 Cyanoalkyl amine (Example No TEPA (28) 0. 5 AgeRite Resin D 1 1 Circosol 2XH 4 l 2. 5 2. 5 Para Flux 2016 2. 5 2. 5 Zinc oxide 3 3 Santocure 1 l Sulfur 2. 5 2. 5 Stearic acid. 1 1 Mooney,ML-4 108 95 Cure at 285 F., min" 1.20 120 300% modulus, p.s.i. 360 500 Elongation, percent. 013 807 Tensile, p.s.i 2,090 2, 530 Hardness e a 64 64 Increase in tensile strength, percent -1 21 Properties at 212 F.:

Tensile, p.s.i 950 880 Elongation, percent 730 525 N 0TE.-For footnotes 3, 4, and 5 see Table 3, footnote 21 see Table 11.

352 Table 33 GR-S 1500 WITH AND WITHOUT POLYACID AND WITH AND' WITHOUT CYANOALKYLAMINE Example No 33-1 33-2 33-3 Compound No B-18491 G-3881 B-6464 Elastomer (GR-S 1500) 100 100 100 S/MAH 2 2 25 25 25 Cyanoalkyl amine (Example No.) 1IP ll 3 AgeRite Resin D 3 1 1 1 Circosol 2XH 4 2. 5

2. 5 3 3 3 2 1 2 1 1 1 0.2 0.2 0.2 2. 5 2. 5 2. 5 Mooney, ML4 50 43. 5 49 Cure at 285 F., min. 60 20 Elongation, percent 480 660 725 300% modulus, p.s.i 1, 360 670 680 Tensile, p.s.i 3,100 3, 165 3, 700 Hardness 63 51 60 Note.For footnotes 2, 3, 4, and 5 see Table 3, footnote 7 see Table 4,

footnote 20 see Table 11.

Table 34 EFFECT OF TWO DIFFERENT CYANOALKYLATED AMINES IN ACIDIC POLYMERS Example No .1

Compound No., B-

Elastomer BD/S/MAA (/23/2) 33 Philblaok O 2 EPA (2-10) 1OH (17) Stearic acidm Oirco-Para AgeRite Resin D Zinc oxide Santocure Increase in elongation, percent N OTE.--F0l footnotes 2, 3, 4, and 5 see Table 3.

33 This is a terpolymer prepared to 59.5% conversion.

Table 35 EFFECT OF CYANOALKYLATED POLYAMINE ON VUL- CANIZATION OF NEOIRENE AND ACID VINYLIC FILLER Example No 35-1 35-2 35-3 Control Compound No., B- 798 796 11408 Elastomer (neoprene) 100 100 Vinylic filler:

S/DVB/MAA 12 20 S/DVB/MAA+BD/VP+resorcinol C11 0 26 Cyanoalkylamine (Example N 0.): 2-

TEPA (220) 1 1 Magnesia 4 4 4 2 2 2 5 5 5 0.75 0.75 0.75 1 1 1 Compound Mooney, ML-4 31 47 79 Cure at 285 F., min 120 120 120 Elongation, percent 925 775 800 300% modulus, p.s.i 435 790 Tensile, p.s.1 2,855 3, 295 3, 630 Hardness 42 70 68 Increase in tensile strength, pcrcent 27 NorE.-For footnote 12 see Table 6, footnote 16 see Table 14, footnote 19 see Table 8.

Ncozone is phenyl-a-naphthylamine sold by E. I. du Pont de Nemours & 00., Inc.

containing acidic vinylic fillers.

the stocks are assured by the use of these amines.

Proper curing times of NATURAL RUBBER CONTAINING ACIDIO VINYLIC FILLERS Example No 36-1 36-2 36-3 36-4 Compound No., B- 1455 18408 18409 18410 Elastomer (natural rubber) 100 100 100 100 Vinylio filler: S/DVB on S/MAH 21 20 20 20 Cyanoalkylamine (Example No.):

3-TEPA (2-1 1 l-TEPA (2-8) 1 l-IP (l-1) 1 Zinc oxide..." 5 5 5 Altax 1 1 1 PBN a 1 1 1 Stearic acid.... 1 3 3 fur 2. 5 2. 5 2. 5 Mooney, ML-4 19 16 12 Cure at 285 F mm. 20 30 20 Elongation, percent 700 735 735 300% modulus, p.s.i 360 415 470 Tensile, p.s.i a. 2, 925 3, 375 3, 670 4, 355 Hardness 32 57 60 63 Increase in tensile strength, percent 15 25 49 NorE.For footnote 27 see Table 13.

b compounded on the cold mill.

In Table 37 one example is given for the use of a cyanoalkylated amine in the vulcanization of a butadieneacrylonitrile copolymer, containing an acidic vinylic filler. The reinforcing effect of the vinylic filler is enhanced by the use of the cyanoalkylated amine.

Table 37 EFFECT OF CYANOALKYLATED POLYAMINE ON VUL- CANIZATION OF BUTADIENE ACRYLONITRILE CO- POLYMER CONTAINING ACID VINYLIC FILLER T lfifmg-For footnotes 3 and 5 see Table 3, footnote 12 see c Hycar 1512-X4 from B. F. Goodrich Chemical Co.

Table 38 shows that the saponification products of cyanoalkylated polyamines can be used in the curing of acidic GR-S 1500 stocks. Although through salt formation of the carboxyl groups with the nitrogen a part of the alkalinity of the amine has disappeared, it is still eiiective in the vulcanization of acidic GR-S 1500 stocks. An increase of 70% of the tensile strength is obtained.

Table 38 EFFECT OF SAPONIFICATION PRODUCT F CYANO- ALKYLATED POLYAMINE ON VULCANIZATION OF ACIDIC GR-S 1500 STOCK Compound No., B- 19446 Elastomer (GR-S 1500) Vinylic filler:

S/DVB/MAA VT/DVB on S/MAH 35 Saponified cyanoalkylamine: (Example No. 2-34) Age Rite Resin D 3 Zinc oxid Stearie acid l Alta); 11 l Capta-x 13 1 Santocure Ethyl tuads See footnote at end of table.

Table 38Continued Example No 37-1 37-2 Compound N 0., B- 11402 11401 Sulfur 2. 5 2. 5 Mooney, ML4 50 50 Cure at 285F., min 60 Elongation, percent 815 525 300% modulus, p.s.i 625 Tensile, psi 1,055 1, 820 50 71 70 Nora-For footnotes 3 and 5 see Table 3, footnote 11 see Table 5, footnotes 12, 13, and 14 see Table (i, footnote 35 see Table 24.

In Table 39 are compared the shelf-lives of compounds of an acidic GR-S 1500 stocks incorporating (a) an amine (Example 39-1), (b) monocyanoalkylated monoamines (Examples 39-2 and 39-3) and (c) a polycyanoalkylated polyamine, Due to the relatively low boiling point, the amines of 39-1 to 3 evaporated out of the stock upon standing, and when the compound was cured after storage of 10 days or more, low tensile strength was obtained. In Example 39-1, the tensile value obtained on compounds cured after storage for 37 days showed 2250 p.s.i. to be compared with 3200 psi. when cured Without storage. Similar behavior is found in Examples 39-2 and 39-3. The polycyanolakylated polyamine because of its relatively low volatility shows better uncured shelf-life. Upon aging the compounded stock for 73 days prior to vulcanization, the tensile strength was only 500 psi. lower than that of the initial value when cured immediately after compounding (3480 vs. 2985 p.s.i.). This can be considered as a good shelf-life.

Table 39 AGING or o R -s STOCK CONTAINING CYANOALKYLATED AMINES Example No 39-1 39-2 39-3 Compound No., B- 2486 2478 2449 18422 Allylamine -1 3 Alpha-allylaminopropionitrile. I1;.%%a-i)propylaminopropionit In conclusion herein are disclosed new compositions of matter including:

(a) Cyanoalkyl polyamines (b) Carboxyalkyl polyamines derived from cyanoalkyl polyamines (c) Resinous materials derived from cyanoalkyl polyamines Further are disclosed that cyanoalkylamines are vulcanization aids for vulcanizable elastomers, especially:

(7) Polar diene elastomers such as polychloroprene and including the vulcanization of these and the resulting vulcanizates.

. as Further disclosed are the use of cyanoalkylamines as vulcanizing aids with fillers including:

(g) Carbon black (h) Polar and non-polar vinylic fillers (i) Inorganic fillers such as the clay fillers, calcium s1hcate and silicon dioxide Included herein are the cyanoalkylamines as vulcanization aids with elastomers and filler in combinations and the vulcanization of such and the resulting vulcanizates.

While there have been described herein what are at present considered preferred embodiments of the invention, it will be obvious to those skilled in the art that minor modifications and changes may be made without departing from the essence of the invention. It is therefore to be understood that the exemplary embodiments are illustrative and not restrictive of the invention, the scope of which is defined in the appended claims, and that all modifications that come within the meaning and range of equivalency of the claims are intended to be 20 included therein.

Iclaim:

1. A vulcanizable composition comprising (a) vulcanizable polymer material selected from the class consisting of natural rubber and synthetic diene polymers containing, ethenoid unsaturation; (b) from about 0.05 to 10 parts of cyanoalkylamine per 100 parts, by Weight, of the vulcanizable polymer material, said cyanoalkylamine being selected from the group consisting of the alpha-cyanoalkylamines and the beta-cyanoalkylarnines and containing only hydrogen, amine-nitrogen, cyanonitrogen and from 2 to 34 carbon atoms; and (c) a filler.

2. Composition of claim 1 in which the vulcanizable polymer material comprises synthetic polymer containing carboxyl groups.

3. Composition of claim 1 in which the filler comprises colloidal sized cross-linked polymer from ethylenically unsaturated compounds and contains groups selected from the class consisting of carboxyl and carbonyl groups.

5 10 parts of cyanoalkylamine per 100 parts, by weight,

of the vulcanizable polymer material, said cyanoalkylamine being selected from the group consisting of the alpha-cyanoalkylamines and the beta-cyanoalkylamines and containing only hydrogen, amine-nitrogen, cyano- 10 nitrogen and from 2 to 34 carbon atoms.

5. Composition of claim 4 in which the vulcanizable polymer material comprises synthetic polymer containing carboxyl groups.

6. In the vulcanization of vulcanizable polymer stock 5 selected from the class consisting of natural rubber and synthetic diene polymers containing ethenoid unsaturation, which polymer stock comprises synthetic polymer containing carboxyl groups, the method of reducing the deleterious effect on such vulcanization of such carboxyl groups that consists essentially in incorporating in the stock a sufiicient quantity of cyanoalkylamine material to substantially reduce such effect, such quantity being an amount by weight of not less than about 0.05 and not more than about 10 parts per 100 parts of said vulcan- 25 izable unsaturated polymer, said cyanoalkylamine being selected from the group consisting of the alpha-cyanoallcylamines and the beta-cyanoalkylamines and containing only hydrogen, amine-nitrogen, cyano-nitrogen and from 2 to 34 carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS 2,439,359 Dixon et a1. Apr. 6, 1948 5 2,697,727 Kaiser et al. Dec. 21, 1954 2,724,708 Williams et al. Nov. 22, 1955 2,743,291 De Benneville Apr. 24, 1956 2,802,806 Doak Aug. 13, 1957 2,809,179 Endres et al. Oct. 8, 1957 

1. A VULCANIZABLE COMPOSITION COMPRISING (A) VULCANIZABLE POLYMER MATERIAL SELECTED FROM THE CLASS CONSISTING OF NATURAL RUBBER AND SYNTHETIC DIENE POLYMERS CONTAINING ETHENOID UNSATURATION; (B) FROM ABOUT 0.05 TO 10 PARTS OF CYANOALKYLAMINE PER 100 PARTS, BY WEIGHT, OF THE VULCANIZABLE POLYMER MATERIAL, SAID CYANOALKYLAMINE BEING SELECTED FROM THE GROUP CONSISTING OF THE ALPHA-CYANOALKYLAMINES AND THE BETA-CYANOALKYLAMINES AND CONTAINING ONLY HYDROGEN, AMINE-NITROGEN, CYANONITROGEN AND FROM 2 TO 34 CARBON ATOMS; AND (C) A FILLER. 